The xPrTiTaO6 (1 − x) YTiNbO6 dielectric ceramic composites are fabricated through the solid state ceramic route. The compositions are calcined in the temperature range 1,200–1,260 °C and sintered in the range 1,350–1,410 °C. Structural analysis of the materials is done using X-ray Diffraction analysis. The composites contain both aeschynite and euxenite orthorhombic phases. The surface morphology of the sintered pellets is examined by scanning electron microscopy. The dielectric constant, conductance and loss factor are measured in the radio frequency region. The UV–visible spectra are recorded and the band gap is calculated. The photoluminescence spectra of the compositions are recorded and the transitions causing emission are identified. The elemental composition of the composites is confirmed using energy dispersive spectroscopy. The materials are suitable for substrate and optoelectronic applications.